JPS60144737A - Photosensitive material for color diffusion transfer process - Google Patents

Abstract

PURPOSE:To effectively restrain fog without lowering sensitivity and developing speed by processing development in the presence of at least one kind of mesoionic 1,2,4-triazolium-3-thiolate compd. CONSTITUTION:A preferable mesoionic 1,2,4-triazolium-3-thiolate compd. is represented by the formula I in which R<1>-R<5> are each optionally substd. 1- about 30, preferably <11C straight or branched alkyl, or 3- about 30, preferably, <11C cycloalkyl or alkenyl, or 1- about 30, preferably, <17C aryl or heterocyclic groups.

Description

DETAILED DESCRIPTION OF THE INVENTION (Field of Industrial Application) The present invention relates to instant photography, and particularly to a novel photographic material for color diffusion and diffusion transfer methods used therein.

(Prior Art) Methods for instantly forming transferred dye images using color diffusion transfer methods are widely known and generally include at least one silver halide emulsion layer on a support and The silver halide emulsion layer is combined with a dye-providing compound,
and identical to the support.

Alternatively, use a photographic film unit (Y) containing an image-receiving layer for fixing a diffusible dye as a color image on another J-th support, and use the two sheet-like photographic elements (a photosensitive element and an image-receiving element or An image is formed by spreading an aqueous alkaline processing liquid between the photosensitive element and the cover sheet.

A developing plate consisting of only one sheet is also known, as described in Netsuron, Japanese Patent Application Laid-Open No. 57-34A.

This type of diffusion paper photosensitive material is an instant photograph.
As exemplified by the phrase, quickly completing an image is the most important thing in terms of product value, so other conventional fi (C
(1) Compared to photosensitive materials, it is required that an image be completed in an extremely short time, and this point is a major feature. For example, in order to complete the image within one minute, silver development must be completed as quickly as possible, within 70 to 75 seconds. This is because the (release and) diffusion of the imaging material following silver development also requires considerable time.

However, it is well known that high-speed development increases and worsens fog, and as is well known, the diffusion transfer method [/
Since a high alkali concentration higher than the specified concentration is used, there is a major drawback in that fog increases significantly. This abnormally high level of fog is due to the fact that high-speed development is required, which is incomparable to conventional photosensitive materials, and development is required under strong alkaline conditions, which is not the case with conventional photosensitive materials. This was a problem specific to the diffusion transfer method. Here, "fog" is caused by silver halide. It means "so-called 1 kaburi" and does not mean "stin".

The shadow caused by such an increase in fog! # is a dye-donor compound (
When using a ``negative color material'', Dmi
Dye-donor compounds with high n that result in staining of white backgrounds, while forming reverse imagewise images for silver images (this is called
When using a positive coloring material), 1dDmaX decreases. The same applies to the complex salt diffusion transfer method.

Therefore, suppression of fog in the diffusion transfer method is a serious problem different from that of conventional sensitive materials, and a solution to this problem has been strongly desired.

On the other hand, as a conventionally known fog suppression method, US Patent No. 3. Kot! , ≠ / -phenyl-!
- Methods using compounds such as mercaptotetrazole, also US Pat.

♂ri♂, U.S. Patent Publication, 00ri, 022, West German Patent Application Publication (UL8) 2. Hirokoa/Za No. 3.

US Patent 3.26! , ≠ A method using a blocked Genbaku inhibitor described in No. 1, etc. or 1% Kaisho Tafu/l1
2≠There is a method using a mercapto compound described in No. 2. However, although the above-mentioned method can suppress fog, it has the disadvantage of significantly slowing down the development speed, and the method that does not delay the development speed has a small fog suppressing effect, which is a contradiction that cannot be avoided.

This contradiction is particularly noticeable in the case of negative emulsions in which the halogenated emulsion forms a latent image on the surface. Does the negative emulsion have surface sensitivity? This is thought to be due to the fact that it is particularly prone to fogging, and the developing speed for fogging is fast.

Furthermore, in the prior art, compounds that suppress fog rarely have the disadvantage of lowering sensitivity.

(Objective of the Invention) The object of the present invention is to obtain a high fCDmax (, Dmin
It is an object of the present invention to provide a photographic material for use in a one-color diffusion transfer method, which has a low color image transfer rate and a fast dye transfer rate to form a color image. Second
An object of the present invention is to provide a color diffusion transfer method that effectively suppresses fog without reducing sensitivity or slowing development speed.

(Structure of the Invention) As a result of intensive studies, the present inventors have found that a support has at least one layer of a halogenated complex emulsion, and the halogenated complex emulsion layer is combined with a dye-providing compound, and a strong An image-receiving layer fixing the diffusible dye (or its precursor) released or derived from said dye-donor compound as a result of development under alkaline conditions is provided on the same or different support as said support. A photosensitive material for a color diffusion transfer method, characterized in that the photosensitive material for a color diffusion transfer method is developed in the presence of at least one type of menion/, , 2.degree. triazolium-3-thiolate compound. It has been found that the material effectively achieves the above objectives.

(Effects of the Invention) According to the present invention, negative coloring material? When using, Dm a
x and Dmin without reducing sensitivity or slowing down transfer speed.
decreases when using a positive coloring material.

It was confirmed that L)max can be effectively increased without the disadvantages of softening of tone and deterioration of sensitivity due to development delay. Such an effect could not be predicted at all from the European Patent (EP) 005≠Hiroshi/Yu Al, which is 1% in the prior art. That is, although the specification of this European patent clearly states that the menion/,j,μ-triazolium-3-thiolate compound used in the present invention is used for photographic purposes, this compound can be developed and fixed by heat treatment. . It is only used as a stabilizing and fixing agent for silver halide used in so-called heat-developable photography. A stable fixer for silver halide forms a water-soluble and non-photosensitive Ag(1) complex upon exposure and processing of a sensitive material, so it can be used even under highly alkaline conditions. ) Processing power 2-
This is fundamentally different from the fog suppression effect in the diffusion transfer method.

(Detailed explanation of the structure of the invention) Menion used in the present invention/2. As a μ-triazolium-3-thiolate compound.

Those represented by the following general formula CI) are preferred.

1□ 几To explain in more detail about the general formula (1) to 1 in the above general formula (1), the substituted or unsubstituted alkyl group of l-L-)L may be linear, branched, or cyclic. ,
In the case of a straight chain or branched chain, the number of carbon atoms in the alkyl group (if the alkyl group has any further substituents, this number is indicated as the number including those.Hereinafter, regarding aryl groups and other groups) (same meaning) is suitably from / to about 30, preferably <l-110 or less. Further, in the case of a cyclic alkyl group or alkenyl group, the number of carbon atoms is suitably 3 to about 30.

Preferably it is 10 or less. The number of carbon atoms in the aryl group or the petero ring is suitably between about 30 and about 30.

Preferably it is 16 or less.

Suitable substituents for the alkyl, alkoxy and alkenyl groups mentioned above include alkoxy, alkoxycarbo
Nyl group, amine group (this includes those substituted with 7 to 2 alkyl groups and cyclic amine groups), alkyl nao group, carbonamide group.

carbamoyl group, carboxyl group, sulfo group, hydroxy group, aryl group (including phenyl group, naphthyl group, and other substituted forms thereof); h heterocyclic residue (j is preferably a membered ring; for example, tetrazole-thalyl, triazolin-3-one-gooyl, etc.), a fluorine atom, and a sulfamoyl group.

Sulfonamide group, -80-R (where H represents a substituted or unsubstituted alkyl group or aryl group), -8
024<R, riB), etc., as appropriate. Also, aryl group, heterotetracycle. Suitable substituents for the acyl group and acyloxy group include the substituents listed above for the alkyl group, as well as nitro groups, halogen atoms, and alkyl groups.

You can choose from aryl groups, cyano groups, etc.

The above-mentioned heterocycle is preferably a 6-membered ring and contains nitrogen, oxygen or sulfur as a heteroatom.Among these, preferred groups are unsubstituted alkyl groups,
Substituted alkyl groups (as substituents, alkoxy, alkoxycarbonyl, carbonamide, carbamoyl, sulfonamide, sulfamoyl), unsubstituted aryl groups (e.g., phenyl), substituted aryl groups (e.g., alkoxycarbonyl as substituents) , a sulfamoyl group, a sulfonamide group, a carbonamide group, a carbamoyl group, a halogen atom, or a phenyl group substituted with a cyano group, etc.); These are the groups listed above.

Next, specific examples of the groups R to l(, are listed below, but are not limited to these.

Specific examples of R1: hydroxy group, methyl group, lauryl group, comethoxyethyl group, ethoxycarbonyl group, allyl group, 2-buten-7-yl group, cyclopentyl group.

Fuclohexyl group, phenyl group, ≠-methoxyphenyl a, s +4L-diprollophenyl group, Hiro-sul 7 amoylphenyl group, 4L-lafuroylamidophenyl group,
2-pyridyl group, /-octylpiperidin-hiro-yl group, acetoxy group, benzoyloxy7 group, methoxy group 1.
2-methoxoethoxy 7 groups, etc.

1 (Specific examples of 2: hydrogen atom, methyl group, imbutel group, tert-butyl group, methylthiomethyl group, cyclopentyl group, cyclohexyl group, phenyl group, lA-methoxyphenyl group, 4cm chlorophenyl group, 2-pyridyl group , caufuryl group, etc.

1 (Specific examples of 3: methyl group, ethyl group, octyl group, octadecyl group, methoxy7ether group, allyl group, coften-yl group,
7 clopentyl group, cyclohexy tv group, phenyl group,
Couetoxycarbonyl 7enyl group, 3-sulfyl moylphenyl group, ≠-methoxyphenyl group, ≠-pyridyl group, copyridyl group, etc.

Specific examples of R4 and R5: hydrogen atom, methyl group, ethyl group, ethoxycarbonylmethyl group, λ-methoxyether group, acetyl group, octanoyl group, phenyl group, cyclophenyl group, etc.

Specific examples of the menion/,λ,1A-)riazolium-3-thiolate compound used in the present invention are listed below, but the invention is not limited thereto.

C113 0211゜031■7 C6H13(n) Kame Ha f-13 113 J13 113 Kame C142(, J:42(JC14,3 (C1(2C-112(J+ 3 C1(3113 CH3 CH3 0C) 13 1-L3 CH3 23℃3)i There are numerous methods of addition, including adding to the silver emulsion layer or layers overlaid thereon (coloring material-containing layer, intermediate layer, protective layer, etc.), adding to the processing solution, adding to the cover sheet, etc. However, it is particularly preferable to add the menion compound of the present invention to the silver halide emulsion layer.

The amount of the menion compound of the present invention added is not particularly limited, but is about 0,
00101 mol is preferable, and more preferably 0.01 mol to λ mol.

When the compound of the present invention is added to a layer other than the non-logogenated emulsion layer, or when added to a processing solution, it is added in an amount commensurate with the above-mentioned amount.

When adding the menion compound of the present invention to the halogenated milk cutting layer, various known methods can be adopted, but emulsion-coating as a water or alcohol solution can be used.
It can be added gradually to the liquid, or depending on the compound, it can be added as an emulsion obtained by emulsifying and dispersing it using an auxiliary solvent and gelate. In particular, the former method is generally used as a prerequisite.5The present invention has made it possible to effectively suppress fog without adversely affecting the development speed and sensitivity of silver halide, making it possible to employ various development acceleration methods. This is also one of the great advantages of the present invention.

That is, as is well known, development accelerators have generally been difficult to use because of their general tendency to increase fogging silver. However, with the effective silver fog suppressing means of the present invention, the generation of silver fog can be significantly suppressed even with the development accelerating means, and as a result, it has become possible to obtain a diffusion transfer photosensitive material in which the surface area is completed very quickly. .

It is also possible to use a known development accelerator in the present invention, and specific examples thereof include alcohols represented by benzyl alcohol, amino alcohols such as aminopentanol, quaternary ammonium salts, These include thioethers, hydroquinones, etc.

Regarding the synthesis of the compounds used in the above claimed invention,
In general ([Anthroacrylation of 1 μm disubstituted naosemicarpazide, (II)≠-Azole/.

≠-Heating of disubstituted thiosemicarbazide, (iii) N-
Reaction of aminoamidine and thiophosgene 1V) Reaction of N-aminoamidine or N-thioacylhydrazine with inthiocyanic acid, reaction of MN-aminoamidine or heteroafluhydrazine with binarized carbon-dicyclohexylcarbodiimide, (vO meso ion/, It can be synthesized by the reaction of 31 μm thiadiazole or the corresponding methioside with a primary amine, etc. More specifically, the compound used in the present invention can be synthesized by the method described in the following documents or the documents cited in these documents. It can be synthesized by W, Baker and W, D, 01
1is.

Chem, lnd, (London), Ri10 (/Tatata): M, (Jhta and H, Kato, in”
INonbenzenoid Aromatics” (J
, P,5nyder,'ed,);,1'.

Potts, S., 1toy and D.P., Jo
nesJ, l1eterocycle, Che, r
n, 2, / 0! (/ri6ri);ni, T, P
otts, 8. ni, 几oy, and D.

P. Jones, J. (Jrg, Cnern,
32, 2.2 uri (/riA7): U, F'
, L) uffin, J., D. Kendall.

and H,L(,,J,Waddington,J,
Chem.

b OC-* J 7 tata (/tata); R, L,
11i'nmannand lJ, 1”ulton, J
, Amer, Chem, Soc.

10, /I Tata (/P Yuza); W, lJ, (Jl
l is/, 222 (/ri7/); W, jJ,
01st s and Trans, I, 633 (/ri74
j);l(,.

Urayshey, fvl, Baumann, and
LL.

Kota 3 (Li 7.2): According to the synthesis method described above, it is possible to synthesize the compound used in the present invention. show.

■Synthesis example 1. Compound 1. Synthesis of 27 g of phenylisothiocyanate and 1.9 g of acetylhydrazine are reacted in ethanol at room temperature to give /-
7 ceterugouphenylteosemicarbazide is obtained. When this was taken in a furnace and heated under reflux in the presence of sodium ethylate in ethanol, 3-mercaptotermeter Gouffe = /l/-/, 2. II-) Riazole is obtained.

/ri, /9 3-mercapdotermethyl-gouphenyl-/,! , μ-triazole was suspended in λθOmQ of methanol and 1.2 g of sodium methylate 2095
Add to this. After lθ minutes, 7 drops of lj9 methyl iodide are added. After 2 hours of reaction, methanol was distilled off and extracted with ethyl acetate to obtain termethyl-3-methylthio-gouphenyl-/
,,! , gatetriazole is obtained.

The obtained termethyl-3-methylthio-guphenyl-
/,,2.4<-) 10g of lyazole and methyl iodide a
Mix and heat to reflux for μ hours.

Since crystals precipitate, they are separated from wP and recrystallized from ethanol. This compound is 1, terdimethyl-3-methylthio-≠-phenyl-7,2. This is Gutriazolicum yoshito.

mp, co/J ~, 2/44'C yield 70% This compound iogyzorm was suspended in pyridine and heated under reflux for 30 hours. Pyridine is distilled off under reduced pressure and ethanol is added to precipitate crystals. This crystal inmr, If also Mass
The spectrum identified it as Compound 1. Collection f1
12. /9 Yield 3, l, % mp,, 2j Ta-23
0'C○ Synthesis Example 2. Synthesis of compound 4/1 μm diphenylthiosemicarbazide/co.

Add to 9 ml and 1 ooIn1 of toluene and stir. Add lauroyl chloride/3.09 to this at room temperature.

After reacting at room temperature for 30 minutes, the mixture was heated and refluxed for t hours.

Toluene after cooling? Evaporate under reduced pressure and dissolve the residue in ethanol. When ammonia hydrate is added to this, colorless crystals are obtained. The crystals were separated by 'kF and recrystallized from chloroform-hexibane. Yield 1k1.7g Yield≠2. t4 mp, 20
j-2C# 'C○ Synthesis Example 3. Synthesis of compound 5 Methyl isothiocyanate 7 J 9 fl j 00
n+1. Dissolve in Nobe/Zen and stir. After adding 7 enylhydrazine/θ1 rlu to this at room temperature, the mixture was heated and refluxed for 5 hours. After cooling, the precipitated gameter-l-phenylthiosemicarbazide kF was collected.

Yield t/-2-29 Yield 67, ≠Imiko≠-Methyl-l-phenylthiosemicarbazide can be used in the next reaction without further purification.

Goomethyl-/-phenylthiosemicarbazide ir, i
g'r'f acid/! OmQ, and 1.2 (heated under reflux for 7 hours. After cooling, the precipitated crystals were taken out and recrystallized from methanol to give the menion Hiroshi-Methyl-/-Phenyl-
/, 2.4A-triazolium-3-thiolate is obtained as pale yellow crystals.

Yield J, J'9 Yield, 20.04 mp, 2117-
KO4AP 0C ○Synthesis example 4. Synthesis of Compound 9 The ≠-menalou/-phenylthiosemicarbazide lza,/9 synthesized in Synthesis Example 3 and the vinegar bar mρ were mixed at room temperature, and anhydrous vinegar g2jmQfz (added thereto, stirred, and heated for t hours. Reflux. Crystals precipitate with the reaction. After cooling, separate the crystals ktP and recrystallize from methanol-acetic acid to obtain compound 7 as colorless crystals. Yield 13.
Yield 6μ, crochet mp, 2 ri O-2 octopus 0CO synthesis example 5. Synthesis of Compound 14 /-phenyl-gumethylthiosemicarbazide 109 synthesized in Synthesis Example 3 was mixed with toluene and mixed with chloride hexafilter 9? at room temperature. c- Add and stir for 30 minutes. Then, heat and reflux for 5 hours.

Toluene is distilled off under reduced pressure, the residue is dissolved in ethanol, and aqueous ammonia is added little by little to precipitate the compound R as crystals. Recrystallize from isopropyl alcohol. Yield G, Og Yield 27. Zari mp, /37-/3ri0C Q synthesis example 6. Synthesis of compound 12 2-methoxyethyl isothiocyanate/l.

7 g was dissolved in benzene and stirred, and phenylhydrazine/1. After adding 9 Y of water, heat to reflux. After reacting for 6 hours, it was cooled and the precipitated crystals were collected in an oven. Yield 66
．． The Hiro-(2-methoxyether)-/-phenylthiosemicarbazide obtained in Section 7 can be used in the next reaction without further preparation.

G<2-Metho'f-'/Ethyl)-/-Phenylthiosemicarbazide is stirred and dissolved in 10.0'ill/jrnll of acetic acid. Acetic anhydride/j is added to this and heated under reflux for ♂ hours. After the reaction is completed, the mixture is cooled, the solvent is distilled off, and the mixture is separated and purified by chromatography using silica gel, followed by recrystallization from isopropyl alcohol-diethyl ether.

Yield t-2, /9 Yield l.

0’lr　mp, 101-10ri0C ○Synthesis example 7. Synthesis of compound 16 μ-ethoxocarbonylphenylhydrazinta.

3g and methyl inthiophanato3. t9f100mρ
dissolves in benzene. Then, the mixture is heated to reflux while stirring. After the evening time, cool and remove the precipitated crystals. /−(≠−
Ethoxycarbonylphenyl)-g-methylthiosemicarbazide is obtained as colorless crystals. Obtained here/
-(≠-ethokizoca/I/bonylphenyl)-≠-methylthiosemicarbazide can be used in the next reaction without further purification.

7-(≠-Ethoxycarbonylphenyl)-
μm methylthiosemicarbazide f/Omu acetic acid plus 10 more acetic anhydrides? After adding, heat to reflux. After the reaction is completed, the mixture is cooled and the precipitated crystals are recrystallized from methanol. Yield g/, r9 Yield Kota, ≠ Chi m p
Synthesis Example 8 Synthesis of Compound 22 r-Bromobutyric acid and 5 times the mole of hydrazine hydrate are dissolved in methanol and heated under reflux for 7 hours. After methanol is distilled off under reduced pressure, the eluted portion is taken by column chromatography using alumina. As an eluent, 11methanol/chloroform/chloroform=202/12 is used. When the eluted portion of the solvent is distilled off, /-aminocopyrrolidino/ is obtained.

109 l-aminocorpyrrolidinone? Dissolve in toluene, add 7.3 g of methyl isothiocyanate, and heat under reflux for 3 hours. After cooling, the precipitated crystal kF is collected and dried. This crystal was identified as L/-(,2-pyrrolidinon-7-yl)-3-methylthiourea by nmr and mass spectra.

Add 1-(2-pyrrolidinone-/-yl)-3-methylthiourea/μgf to 20 mQ of acetic acid and stir. Then 20m1. Add acetic anhydride and heat to reflux. After the reaction is completed, the solvent is distilled off and recrystallized from ethanol. Yield 3.
≠9 Yield,! 7. /4mp, 2tough, 2t0C The silver halide emulsion used in the present invention is a hydrophilic emulsion of silver chloride, silver bromide, silver chlorobromide, silver iodobromide, silver chloroiodobromide or a mixture thereof. It is a colloidal dispersion that can have various halogen compositions, but has an iodide content of 10 molar or less,
Silver bromide, silver iodobromide or silver chloroiodobromide having a chloride content of 30 molar or less is particularly preferred. The silver halide emulsions used in the present invention may have color sensitivity extended by spectral sensitizing dyes, if desired. As the spectral sensitizing dye, cyanine dyes, merocyanine dyes, etc. can be used as appropriate.

Internal #retention silver halide emulsions can also be used in the present invention, examples of this type of emulsion include, for example, US%ff2° tag 1. ,2
No. 10, same 3. ．． ZOt, 3/3 issue, same 3, ≠ Ko 7, 2
．． No. 27, J, 7&/, 27J, and 3. ri3
Conversion type emulsions, core/shell type emulsions, emulsions incorporating different metals, etc., which are described in the QL issue and the like, can be mentioned.

Among the above-mentioned silver halide emulsions, high-speed negative emulsions that form surface roughness are particularly useful in the present invention, and conventionally known high-speed negative emulsions can also be used. These negative emulsions include Re5earch Disclosure.
eA, 2 J, Yu 3 Hiro (/ Riza 3), West German clock application <(
JLS)s, 2≠/, &≠2AI, etc. tabular grains (
An emulsion containing silver halide grains (Tablet Grain) is also preferably used.

As mentioned above, surface latent image type emulsions exhibit a marked increase in fog in the diffusion transfer system, so it is thought that the effects of the present invention are particularly noticeable. In addition, the surface latent image type emulsion has the root part (
It was found that the difference in development speed between the area with the largest amount of silver deposition and the non-exposed area (1dI9r with the smallest amount of silver deposition) was small. It was found that it is more effective to include it in

Among these, it is preferably contained in a red-sensitive emulsion layer (an emulsion imparted with red sensitivity by a trimethene cyanine sensitizing dye) or its vicinity.

Immobile dye-providing compounds (colorants) that release diffusible dyes (including their precursors) as a result of development under alkaline conditions are negative-working.
ng) It may be a coloring material, or it may be a positive type (Posit
(live-working) coloring material may be used, but the latter is preferable for the purpose of creating a positive transferred dye image.

A typical negative coloring material is an N-substituted sulfonamide redox compound that releases a dye upon oxidation and subsequent hydrolysis.

On the other hand, examples of positive coloring materials that can be used in the present invention include US Pat.

No. 312, Same Gu, / Tata, 3! gu issue, same gu, l tata, 3
! Evening issue, Douhiro, 37/, 60 Hiro, Tokukai Akihiroter///
No. 1,21, t/-434/r %-1 λ
−≠Za/ri, same evening 3-6203 J, same tagu/
30 Octopus No. 7, same tough-//ri 3hiro! No., Tokugan Showa r-
Examples include compounds having a positive redox core described in +o Kozarigoji.

In particular, the positive coloring material suitably used in the present invention is an immobile coloring material that releases a diffusible dye by accepting at least one electron, and this compound is a diffusion-resistant electron donating compound (hereinafter referred to as "ED"). This HD compound is a strongly reducing compound or its precursor present in the emulsion layer or a layer adjacent to the emulsion layer, and specific examples include, for example, U.S. Patent No. 271,730. No., Dohiro, No. 263,323, Tokukai Showa 4-/JJ'73
It is stated in the issue etc. Inclusion of such HD compounds in the emulsion layer or its vicinity is also a cause of increased fogging silver in the halogenated emulsion, and this ED
The present invention also exhibits an even more remarkable effect in suppressing silver fog caused by compounds. Naturally, even if a coloring material and an ED compound were integrated, that is, a coloring material having the function of an EL (EL) compound in the same molecule was used, the fog silver was increased in the same way.

Among these, particularly preferable specific compounds include those having the following structures, but the present invention is not limited to these coloring materials. Further, a type having a positive redox core and an HD compound built into the same molecule is also suitable in the present invention.

In addition, a dye developer that diffuses under alkaline conditions can also be used as a positive coloring material.

The dyes formed from the colorants used in this invention may be ready-made dyes or may alternatively be dye precursors that can be converted into dyes in photographic processing steps or additional processing steps, with the final image dye being a metallic dye. May be complexed or not. Representative dye structures useful in the present invention include metal-complexed and non-metal-complexed dyes such as azo dyes, azomethine dyes, anthraquino/dyes, and phthalocyanine dyes. Among these, azo cyan, maze/yellow and yellow dyes are particularly important.

Next, to give examples of the dye moieties used in the present invention, including specific examples as negative-tone coloring materials, these dye moieties can be combined with positive-tone redox cores as long as the connecting part is changed. Can be easily used as a positive coloring material.

Specific examples of yellow coloring materials include Tokko Sho≠2-2tIt No.; US Pat. No. 3,302,722, and Tokko Sho Tough-72141.
No. 0, Japanese Patent Application Publication Showa/-1141P30, Sameta ≠-///
J Hiromu No., J [-/l/30, Dota 4-71072
No. j≠-72031, No. 3-6≠036 and 5 μm23! , No. 27: US Patent RI, /≠r, +≠
Same as l≠, l≠za.

A u 3 ; kResearch Disclos
ure/7 A3.

(lli71.) No. 11A7j (!F77).

Also, specific examples of the magenta coloring material are U.S. Pat. θ issue and Tokukai Sho! Co. No. 106,727: U.S. Patent 3. 3x, 3ro
No. 3. ri3/, /u4A, same 3. Ri3ko, 301
issue, JP-A-10-1/Tata 2♂, same evening λ-1067,
No. 27, J3-Co3T Ko♂ No., Tag-4103≠ No., Tata 5tro≠ No., j'μ-/6133λ No.
Same J′! -1A0.21 issue, tj-730!7 issue, Taro 71060 issue, Tata/3≠ issue, same tag -41
03≠, U.S. Pat.

, 2za79.2 octopus, same≠, 3!7, ≠10,
Same≠, 3 tough, 4t/2 No.

Furthermore, a specific example of the cyan coloring material is Tokko Sho≠J'-3
2/30 issue, JP-A-Shota 2-4♂, 27 issue, 4! Tar/
, 2t33/issue, j/-109921, rp-tata≠31, t3-/≠73r, rp-rx
No. Z, No. 413-177123, same as J-/G33. Z
No. J, Tata≠-Tata≠31, tG-7104/, No. 13-6'103 and Tagu/Co//2, U.S. Patent≠, l-λ, Zari No. 1, same Hiro, / Tata, Tata μ,
Dohiro, /4A7゜Yuhiro≠ issue, same≠, /gu♂, 6μ2 issue,
European 7R Patent No. J3,037, 13, 011-
No. 0; Re5earch IJisclosure /
7, t 30 (/27g) issue, and the same/&, da 7
It is written in the evening issue (/ri 77).

Furthermore, as a type of dye precursor, a dye-releasing redox compound having a dye moiety that temporarily shifts light absorption in a photosensitive element can also be used in this patent;゜No. 330, same tar-! 33
Kota No., U.S. Patent No. 3゜336.217, J, j7
F, No. 3344, 3.2 Za2. Tag No. 6, British Patent/, Doug 6f, No. 17.

As the developer used in the present invention, any silver halide developer can be used as long as it undergoes cross-oxidation with a desired compound (coloring material, ED compound, etc.). Such a developer may be included in the alkaline processing composition or in an appropriate layer of the light-sensitive material. Examples of developing agents that can be used in the present invention are as follows.

Hydroquinones, aminophenols, phenylenediamines, pyrazolidinones [e.g. phenidone, l-m-tolyl-μm] described in JP-A-/1, /J/
Dimethyl-φ-methyl-3-pyrazolidinone in hydro,
Dimezone, 7 mether-3-pyrazolidinone in 1-p-tolyl-≠,≠-dihydro, "-p-tolyl-≠-methyl-μm hydroxymethyl-3-pyrazolidinone, /-(
[methoxyphenyl]-μm-methyl-hydroxymethyl-3-pyrazolidinone, l-phenyl-gumethyl-≠-hydroxymethyl-3-pyrazolidinone], and the like.

Of those listed herein, black and white developers (among them pyrazolidinones) are particularly preferred as they generally have properties that reduce stain formation in the image receiving layer more than color developers such as phenylene diamines.

The processing composition used to process the photographic light-sensitive material of the present invention preferably contains a base such as sodium hydroxide, potassium hydroxide, sodium carbonate, or sodium phosphate and has a pH of about 10% or higher; It preferably has an alkaline strength of I/ or more.

The treatment composition may contain antioxidants such as sodium sulfite, ascorbate, piperidinohexose reductone, and may also contain silver ion concentration regulators such as potassium bromide. It may also contain viscosity increasing compounds such as hydroxyethyl cellulose and sodium carboxymethyl cellulose.

Further, the alkaline processing composition may contain a compound, such as benzyl alcohol, which has the effect of promoting development or promoting dye diffusion.

When the photosensitive material of the present invention constitutes at least a part of a film unit consisting of a photosensitive element, an image receiving element (these elements may be integrated), a processing element (processing composition), and optionally a cover sheet, The treatment composition is described in U.S. Pat. No. III, same, 6μ2. rrt number, same λ, 613°73.2, same number, 7+23. Ot1,
Same 3.0 Tat, Hiro 1, Same 3.0j &, ≠ Tar, Same 3゜lriλ,! It is preferable to use the container by filling it into a container that can be ruptured under pressure, such as those described in No. lt.

Selective spectral sensitivity in a certain wavelength range for natural color reproduction by subtractive color method? A light-sensitive material is used, which is composed of at least two combinations: an emulsion with spectral absorption and a coloring material with selective spectral absorption in the same wavelength range. .

In particular, light-sensitive materials comprising a combination of a sensitive silver halide emulsion and a yellow dye coloring material, a combination of a green-sensitive emulsion and a magenta coloring material, and a combination of a red-sensitive emulsion and a 717 coloring material are useful. The combination of these emulsions and coloring materials may be coated in a layered manner in a face-to-face relationship in a Fi light-sensitive material, or may be coated in the form of individual grains (coloring material and silver halide grains are present in the same grain). ) may be mixed and applied as a single layer.

Scavengers for oxidized developers can be used in various intermediate layers of the light-sensitive materials of the invention.

Suitable materials are described in Research Disclosure, Volume iri (January 1976), pages 76-72.

JP-A Show Tatata λO! between the intermediate layer and the layer containing the coloring material.
A separating layer may be provided as described in No. 6. Further, a silver halide emulsion may be added to the intermediate layer as described in JP-A-14-47fftO.

Regarding the mordant layer, neutralization layer, neutralization speed control layer (timing layer), etc. that can be used in the light-sensitive material for the color diffusion transfer method of the present invention, for example, as described in U.S. Pat. things can be applied.

Using the photosensitive material of the present invention, p-color photographs can be obtained through the following steps.

That is, the photosensitive material (or photosensitive element) is exposed imagewise.

Next, a developer (electron transfer agent) and the menion of the present invention/,
, 2. The processed silver halide emulsion is developed by processing with an alkaline processing composition in the presence of a ≠-triazolium-3-thiolate compound.

The development of the silver halide emulsion then results in the formation of an image-forming distribution of diffusible dye, and then the diffusion (transfer) of at least a portion of this dye into the image-receiving layer (or image-receiving element).
let

This results in a diffusion-transferred color image on the image-receiving layer.

Further, by the same method as above, color photographs can also be obtained by utilizing the dyes remaining in the light-sensitive material (or light-sensitive element).

As mentioned above, the light-sensitive material of the present invention primarily consists of a light-sensitive element (1) in which at least one silver halide emulsion layer is coated on a support, but it also comprises a light-sensitive element (1) and an image-receiving element (or Embodiments in which image-receiving layer) (2)' is combined are also included in the present invention.Furthermore, a means for supplying processing composition (3) is added to form a photosensitive material (i.e., a film) consisting of (2) and (3). units) are also included within the scope of the present invention.

In the embodiments including (1), (2), and (3) above, the container for supplying the processing composition is arranged such that the contents (processing composition) are placed between the photosensitive layer and the cover sheet, or between the photosensitive layer and the image receiving layer. It is arranged so that it is supplied between the layers.

The image-receiving element described above may be placed on a separate support so that it is superimposed with the photosensitive element after exposure.

Such embodiments are described, for example, in US Pat. No. 3,362. It is described in the tl. Also, as a variation of this, this Uke Il!
The element may be superimposed with the photosensitive element throughout before, during, and after exposure.

Alternatively, the image receiving element may be provided on the same support as the photosensitive element. Such an integrated form (film unit) is known, for example, from Belgian patent 7!7. ri6Q
A variant of this is also described in Belgian Patent No. 7, No. 7, R.

As a further variation of the integrated configuration, a release layer may be provided between the image-receiving layer and the photosensitive element. As a result, after forming a transferred image, the photographer can peel it off as needed and use it as a normal color print or color slide.

Example 1 A laminated integrated color diffusion transfer photosensitive sheet Ifx/''-1, a cover sheet, and a processing solution were prepared as follows.

Preparation of photosensitive sheets: Each layer was coated on a polyethylene terephthalate J-light support in the following order to prepare photosensitive sheets 7-t/-t.

(1) Copoly[styrene-N-vinylbenzyl-N-
Methyl-piperidinium chloride]3. Q97m”
, an image-receiving layer containing 3.0'j/m2'l of gelatin.

(2) Titanium dioxide 2097m, gelatin 2. Qg/m
White reflective layer containing 2W.

(3) A light-shielding layer containing carbon black, O'i/m, and gelatin/, 097 m.

(4) Below (D-777 color material/, !x/, Omol/m
2. The following HD compounds kl, jXlo 'mol
7m”, N, N-diethyl laurylamide 0,
/ 9 / m” and gelatin 0, J' 97
layer containing m2.

R= (5) Amount of red-sensitive surface latent image type silver iodobromide, l.

09/m2), the compound shown in Table 7? 0.02mol
/mol Ag,N,N-diethyl laurylamide 0.0/97m” and gelatin 0,A
$)/m2.

(e)2. j-di-t-pentadecylhydrokino 7 (
7, evening g/m2, gelatin 0. Hiro1)/m2f? r: Containing layer.

(7) The following structure Tsuma center color material - 2X / 0' m
ol/m2, the following ED compound AJX/(7'mol/
m”, N, N-diethyl laurylamide θ, 19/m
A layer with 2% and U Ceratene o, r g 7m29t4.

几 = (8) Green-sensitive surface latent image type silver iodobromide emulsion (silver i, og7
m2), Compound o, 0/mol shown in Table/
/mo IAg, N, N-diethyl laurylamide 01
01g/m2, and gelate 70, A9/r
layer containing n2f.

(9) Same as layer (6).

Trout Yellow coloring material JX/0'mo with the following structure
l/m2, below ED compound A J x / 0 'm
o l/m2, N.

Layer containing N-diethyl laurylamide 0./g/m and gelatin 0.19/rn2.

几＝ （￥ Blue-sensitive surface latent image type silver iodobromide emulsion C＠/,,097
m2), compound O0θθjmol/mol shown in Table 1
Ag, N, N-diethyl laurylamide (7,0/'
i/rn, layer containing gelatin 7 (7, Ifj 7m2.

(b) Polymethyl methacrylate latex (average particle size μμ, o, tog/m ), gelatin (/, 0
g7m ) and a protective layer containing triacryloyltriazine (0,0λ9/m ) as hardener.

A cover sheet was prepared by sequentially coating the following layers (1') to (3') on a transparent polyethylene terephthalate support.

(/') to pair of acrylic acid and butyl acrylate, zO
(weight ratio) copolymer (129/m ) and □l, u-
Bis(co,3-epoxypropoquine)-butane(0,4
'4' 97m).

(J/) acetylcellulose (which hydrolyzes IOOG's acetylulose to produce 3F,'19 acetyl group) (3,♂9/m ) and 60 pairs of styrene and maleic anhydride ≠O ( (weight ratio) copolymer (molecular weight approximately! 10,000) of methanol ring-opened product CO, J3g/m2)
and! -(nocyano-l-methyletherthio)-l
- a layer containing phenyltetrazole (θ, /month q/m ).

(3') μ2.7 pair of styrene-n-phthyl acrylate-acrylic tl-N-methylolacrylamide≠
2.3:3:3 (weight ratio) copolymer latex and 23:μ:3 (weight ratio) copolymer latex of methyl methacrylate-acrylic acid-N-methylol acrylamide, the former latex and the latter latex. Solid content ratio is 6
A layer with a thickness of 0.0 μm is mixed and applied so that it is symmetrical.

ED compound A) 0 CCHa H Compound D (for comparison) As is clear from the table, the photosensitive sheets λ to l of the prior art
Although this method has the effect of suppressing darkening (Dmax up), it has the disadvantages of a large decrease in sensitivity (refer to the shadow sensitivity value) and a large decrease in development speed (softening of the tone, that is, a decrease in r). It can be seen that the photosensitive sheet of the invention has excellent properties such that there is substantially no decrease in sensitivity, and the development speed is not delayed (no softening of tone). K effectively suppresses fogging.

Example 2 In order to confirm the improved effects of the present invention, the following photosensitive sheets and image receiving sheets were prepared.

Photosensitive sheet (4,2~/evening) A photosensitive sheet was prepared by coating each layer on a polyethylene tere-7 tallate support as follows.

Punk side = (a) Carbon black, O″g/m2
, gelatin 2, Og/m2.

Emulsion layer side: (1) 10' mol of the following coloring material
/m2, ED compound AJx/(7'rnol/m2, N,N-diethyl laurylamide 00 1 g/m2, gelate y/9/m''f) used in Example 1.

(2) Red-sensitive surface latent image type silver chloroiodobromide emulsion (α:Br:l
=Ko θ near! 2), an emulsion layer containing /97 m in the amount of silver, the compounds shown in Table 2 in the amounts shown in Table 2, and 1 g/m2 of gelatin.

(3), 2. tert-pentadecylhydroquinone/9/in and gelatin O2!97m
A layer containing.

(4) Gelatin 0.2g/m f! : Containing layer.

Image-receiving sheet paper support: /jOμ thick paper laminated with 30μ polyethylene on both sides.

In the polyethylene on the image-receiving layer side, titanium oxide having an IT value of 10176 is added to the polyethylene in a dispersed manner.

Pack side: (a) Carbon Black II, 097m
2. Gelatinco, 097m2 of light-shielding layer.

(b) Titanium oxide 1.0g7m2, gelatin/
Og/in2 white layer.

(C) Protective layer of gelatin O, t9/m2.

Image-receiving layer side: (1) Neutralization layer containing -297 m2 of acrylic acid-butyl acrylate (molar ratio t:co) copolymer with an average molecular weight of o, ooo.

(2) Acetylation degree! 1.3 (weight of acetic acid released by hydrolysis per sample/g) 0. ! /3'i) and a styrene-maleic anhydride (molar ratio i:i) copolymer with an average molecular weight of about io, ooo in a ratio of tata to yen, μ, 1 ti 7 m2 Neutralization timing layer.

(3) Styrene-butyl acrylate-acrylic acid-
Polymer latex was emulsion-polymerized with N-methylol acrylamide in a weight ratio of 7/412.3 /H/≠, and methyl methacrylate/acrylic acid/N-methylol acrylamide was emulsified in a weight ratio of 23:3:≠. A layer containing polymerized polymer latex blended at a solid content ratio of 7/m2 to 49/m2.

(4) The following polymer J, 097m2 and gelatin J
, 09/m"?: An image-receiving layer coated using a coating aid.

x:y:z=evening:! :ri0 (5) Protective layer coated with gelatin 0, A 97m2.

Processing Solution After the photosensitive sheet was exposed through a color test chart, the image-receiving sheet was placed on top of the other, and the processing solution was spread between the two sheets to a thickness of tigμ.
The expansion was done with the help of a pressure roller).

Treatment i1' was carried out at 0C, and the photosensitive notebook and image-receiving sheet were peeled off 90 seconds after the treatment. Table 1 shows the results of measuring the reflection density of the image receiving sheet.

As is clear from Table 1, in the photosensitive material using Comparative Compound E, when a large amount is added, Dmax increases, but the sensitivity decreases significantly, whereas in the photosensitive material of the present invention, Dmax is sufficiently small. ? It can be seen that this is an extremely excellent photographic material with almost no decrease in sensitivity and no softening (in fact, an increase in contrast) even when added.

Patent Applicant Fuji Photo Film Co., Ltd. Procedural Amendment January 1985 71-1 Dear Commissioner of the Patent Office 1, Indication of Case Showa! Patent Application No./AJg No. 2, Title of the invention Photographic light-sensitive material for color diffusion transfer method 3, Relationship with the case of the person making the amendment Patent applicant 4, Subject of the amendment ``Detailed description of the invention'' in the specification Column 5: The description in the "Detailed Description of the Invention" section of the description of contents of the amendment is amended as follows.

/) No. 1/page 77 to /2 line “..., and among R2, it is preferable...”
It is the basis. " is corrected to ". At least one of R1, R2 and R3 is a substituted or unsubstituted phenyl group, and it is preferable that the total number of carbon atoms in R1-R3 is 7 or more."

that's all

Claims (1)

[Claims] l) at least one silver halide emulsion 1- on a support;
and the silver halide emulsion layer is associated with a dye-donating compound and contains a diffusible dye (or its Precursor) fjr: A photographic material for a color diffusion transfer method having an image-receiving layer to be fixed on the same or a different support from the above-mentioned support, containing at least one type of menion 1, 2, . 1. A photographic material for color diffusion transfer, characterized in that it is developed in the presence of a II-triazolium-3-thiolate compound. 2) The color according to claim 1, wherein the halogenated steel emulsion is a surface latent image type emulsion (negative emulsion), and the dye-providing compound is of a type that gives a positive transfer dye image. Photographic material for diffusion transfer method. 3) The dye-donating compound accepts at least one electron as a result of development under strongly alkaline conditions to form a diffusible dye (
a non-diffusible redox compound that releases a non-diffusible electron-donating compound (or its precursor), and is this compound further combined with a non-diffusible electron-donating compound. or an electron-donating group (or a precursor thereof).